N, n-ethyleneureido esters of acrylic and methacrylic acids



Patented Aug. 17, 1954 UMTED N lSTA-'lf15S PATENT l OFFICE mNm'rnrLENEU-REIDO Estrnrts o F scarno n l l ANn-Mmrmcruefnoms Newman M Bortniok, 'Orolonl Pa assigllor to Bohm At Haas Company, Rliiladolha, Pa., a corporation of `Delaware,

l Y Dray/fing. ApplicationuApril 10, 1953,

l n l ,Serial No. 348,101A

The Aloyer.ltior relatos to lpoly.:tlorlzalole oom- 'pounds having thelgeneral formula t in which R represents a hydrogen atom `or a methyl group, and A represents an alkylene group; i. ,e, a saturated, divalent, aliphatic hydrocarbon group. This invention also relates to .the YY11amopJlzvlnol'sof those .compounds and to eQpQlymersof .thecompounds and other copoly- ,merizable compounds Which ,contain at i.least 4,one

vinylidene group, CH2= Zlhe Acoma@mds of this invention innovare-d by reacting ethylene.mino .with ,an .lsooyauato ester of acrylic or methacrylic acid according to the following representation in which the' characters, R and A, have the sig-o niiicance described above.

The isocyanato esters wloh` :are :employed herein :are themselves the subject of another of my applications for Letters Patent, Serial No. `319,603,'flled'November-81951 t l It istdbe noted thatthey allylenegroups, which are represented "by the character A above,` remain intact during the reaction. Compounds in which the `alkylene group, A, contains tWo to fourteen carbon atoms in straight lor branched chains arelprepared in this way from the corresponding isocyanato esters. The products Which-havelbeen most-satisfactory;r however, `from the standpoint of ease of polymerizationand l copolymerization and which have been most use-` Essl-persulfate .andammonium -orborata 2 Y??? SL19@ bGHZQQMtOI-u Xyleg 99111231.18 andttllo ,l-ilso lo rooomllll, oli

The compounds of this invention undergo ladditioa oolylaotlzatlon alone' and Witt.1 otllor .oomaoullllsoootololoe a ylllyllolono stoop, CH2FC .511th nolyimorizatoo ,ooo loo` oofrlodout in .bulk solution or lo ,om sloo- Emolsiorlo of ooooly, ,oro ooftioolorly yoloololo ,for 'ooo ,lil tho Shrink-,molino of wool.

`axonnoloo :of oorolymorlzeblo metorialo Whioh sly@ .riso to thermoplastic oooolymoro Wltll tho rrofluoto of? .o loyootlorl lnolodlo tho ,following N-.olalk-.yl oorylalelooo oooh oo dimethyl .oorylamide and diethyl acrylamide; esters .,oacrylic, U-Iolllotooorfyllo and mothootyllo .ooiolo oooh oo m thyl -aoyyloto otllyl aorylatol 2othy1ho2 y1 ylate .roothylloothoryleto tort-butyl mothacrylate. octyl methacrylats, butylA chloro- -acrylates and lauryl chloroacrylate; vinyl hydrolcarbqnssuthaststytoxla tznlothylotytoool ylrlyl- -nanthalonozand--tyloyltoluorlo; orllltalld vinylidene chloride; allylA i:31,5151 lnjletldral-lyl lesters of saturated aliphatic carboxylic acids suchas allyl aoototo .allo .mothtlllyl orololollatot oorylonitrile;vinylpyridine;andlthdikel It should also be pointed out that the products of this invention aro also oopolylllorlooblo With compoundsY like divinylbenzene, trivinylbenzene and diallyl phthalate, which contain a plurality of vinylidene groups but that the vrresultant copolymers. are cross-linked and consequently non-thermoplastic;

The compounds of this inventio'nu Acan be srolloolnlooollmoororooloooloofftlio'lool foooolymot- Polymotloatlooaod foopolymorlzatloo of the u l, f this invention arebthaciratedjby tloo ooolohoetollt ,yiolot holt'fftoo-tad'oal ,ooftalyoto Tho following `elio tyololol' of Soltololo `catalysts: `auf:lois-,azolsolootyon llo, mothyl aooloooutyrato looezoyl elo-roxy., lfooty'l Pior- "oizid/e, 'lauroyl peroxide, tert-butyl `hyd"ropllfQ- ide, idi-tertfbutyl perogide, tert-butyl ,perbenooiootlahymm nlllln f'lllsclll' oxido, and floorfsaltot 3 alysts are used in amounts from 0.01% to 5%, and preferably from 0.02% to 2%, based on the weight of the polymerizable compounds.

The following example is presented as embodying the preferred process for making the new N,'Nethyleneureido esters of this invention.

Example 1 Into a three-necked ask equipped with thermometer, mechanical stirrer and reiiux condenser was charged a solution of 77.5 parts (0.5 mol) of beta-isocyanatoethyl methacrylate in 1000 partsof pentane. To the stirred solution was added slowly 21.5 parts (0.5 m01) of ethyleneimine while the temperature was maintained between C. and 20 C. by means of external cooling. The reaction mixture was stirred for an hour after the addition of the ethyleneimine. An oily layer separated. The pentane was pumped off at 0-15 C. under reduced pressure. A 94% yield of N,N-ethyleneureidoethyl methacrylate was thus obtained and its structure was confirmed by analysis.

The product polymerizes very readily, especially at temperatures above 50 C., even in the absence of a peroxidic catalyst. Such polymers are insoluble in most common solvents and merely swell on immersion in methanol or ethanol.

The other esters of this invention are prepared in the same way. Temperature is a most 4important factor and it is recommended that 'the temperature be held below about 20 C. in

order to avoid loss of the monomeric esters by polymerization.

The following example is presented in order.

to `illustrate the preparation and use of copoly- `mers containing the compounds of this invention.

Example 2 The following components were placed in a. 500 ml. flask equipped with a mechanical agitator and thermometer:

Y 97 parts of ethyl acrylate 8.6 lparts of non-ionic dispersing agent (a 70% aqueous solutionbf a tert.octylphenoxypo1y ethoxyethanol) The contents of the flask was cooled to 15 C. Vand then was added an aqueous solution con-r taining 0.12 part of ammonium persulfate and 0.16 part of sodium hydrosulte. The mixture was agitated. After about 7 minutes, an exothermic polymerization reaction began and the temperature rose to 47 C. at which point an icebath was, applied in order to maintain the ternperature between 42 and 45 C. In 8 minutes the reaction subsided but agitation was continued until the emulsion cooled to room temperature. When the emulsion was flowed on a glass or metal panel and dried at 100 C., it gave a lm which had excellent resistance to toluene and water. A determination of the amount of nitrohad copolymerized in the ratio of 97% of the former to 3% of the latter.

The same procedure was followed in the production of an emulsion containing a copolymer of 95% ethyl acrylate and 5% N,Nethyleneure acavv 4 idoethyl methacrylate. A lm laid downfrom this emulsion was even more resistant to toluene than the one described iirst.

In a similar way a mixture containing by weight of butyl acrylate and 5% N,Nethylene ureidoethyl methacrylate was emulsied and polymerized. Still another emulsied copolymer of 95% 2ethylhexy1 acrylate and 5% N,Nethyl eneureidoethyl methacrylate was prepared in a similar fashion.

All of vthese emulsions had real value in the shrink-prooiing of wool when they were padded on woolen fabric and heated to' a temperature of 240 F. or higher. The copolymer of butyl acrylate had less harshening eiect on the wool than did the copolymers of ethyl acrylate, while the copolymer of 2-ethylhexyl acrylate did not perceptibly alter the hand. In standard comparative wash tests,

wool treated with the emulsions described above and heated for 10 minutes at 300 `1l'. shrank less than 5% after a 300 minute laundering while untreated woolen blanks invariably shrank to about one-half their loriginal dimensions.

I claim: 1. Polymerizable N,Nethyleneureido having the general formula esters in which A represents an alkylene group containing 2 to 3 carbon atoms.

3. Polymerizable N.Nethyleneureido esters of methacrylic acid having the general formula in which A represents an alkylene group containing 2 to 3 carbon atoms.

4. N,Nethyleneureidoethyl acrylate having the formula 5. yN,Nethyleneureiezloethyl methacrylate having the formula CH2 onz=o cHa cooozHiNH-co-N/i 4 \CHE2 6. A polymer of an N,Nethyleneureido ester which has the general formula oH2=o Ro o o-A-NH-c o-N/ .in which Ris a member of the class consisting of a hydrogenV atom and a methyl group and A represents an alkylene group containing 2 to 14 carbon atoms.

7. A copolymer containingia) at least V1%, on

a molar basis. of a copolymerized N,Nethyl n eneureido ester having the general formula in which R is a member of theclass consisting of a hydrogen atom and a methyl group and A representsanalkylene group containing 2 to 14 carbon atoms and (b) at most 99% of a copolymerized compound which is different from said N,Nethyleneureido ester and which contains a vinylidene group, CH2=C 8. A copolymer containing (a) 2% to 20%, on a molar basis, of copolymerized N,Nethyleneure idoethyl acrylate and (b) 98% to 80% of copolymerized ethyl acrylate.

9. A copolymer containing (a) 2% to 20%, on

6 a molar basis, of copolymerized N,Nethy1eneure idoethyl methacrylate and (b) 98% to 80% of copolymerized ethyl acrylate.

10. A copolymer containing (a) 2% to 20%. on a molar basis, of copolymerized N,Nethyl eneureidoethyl acrylate and (b) 98 to 80% of butyl acrylate.

1l. A copolymer containing (a) 2% to 20%, on a molar basis, of copolymerized N,Nethylene ureidoethyl methacrylate and (b) 98% to 80% of butyl acrylate.

12. A' copolymer containing (a) 2% to 20%, on a molar basis, of copolymerized N,Nethyl eneureidoethyl methacrylate and (b) 98% to 80% of octyl acrylate.

No references cited. 

1. POLYMERIZABLE N,N-ETHYLENEUREIDO ESTERS HAVING THE GENERAL FORMULA 